Compositions Containing Diesel and Fatty Acid Methyl Ester/Maleic Anhydride/Esters (FAME/MA/Esters) and the Use of FAME/MA/Esters to Improve the Lubricity of Diesel

ABSTRACT

A composition containing diesel (e.g., containing less than about 15 ppm sulfur) and fatty acid methyl ester/maleic anhydride/esters (FAME/MA/esters), wherein the FAME/MA/esters are prepared by a method involving reacting FAME with MA to form FAME/MA and reacting FAME/MA with alkyl alcohol to form FAME/MA/esters; wherein the FAME is conjugated. The FAME/MA/esters are produced from tung oil or from plant oils in which the unsaturated fatty acids have been converted to conjugated fatty acids. Also a method of improving the lubricity of diesel, involving combining diesel and FAME/MA/esters, wherein the FAME/MA/esters are prepared by a method involving reacting FAME with MA to form FAME/MA and reacting FAME/MA with alkyl alcohol to form FAME/MA/esters; wherein the FAME is conjugated.

REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Application No. 62/733,774, filed 20 Sep. 2018, which is incorporated herein by reference in its entirety.

BACKGROUND OF THE INVENTION

Disclosed herein are compositions containing diesel (e.g., containing less than about 15 ppm sulfur) and fatty acid methyl ester/maleic anhydride/esters (FAME/MA/esters), wherein the FAME/MA/esters are prepared by a method involving reacting FAME with MA to form FAME/MA and reacting FAME/MA with alkyl alcohol to form FAME/MA/esters; wherein the FAME is conjugated. The FAME/MA/esters are produced from tung oil or from plant oils in which the unsaturated fatty acids have been converted to conjugated fatty acids. Also disclosed are methods of improving the lubricity of diesel, involving combining diesel and FAME/MA/esters, wherein the FAME/MA/esters are prepared by a method involving reacting FAME with MA to form FAME/MA and reacting FAME/MA with alkyl alcohol to form FAME/MA/esters; wherein the FAME is conjugated.

Recently, the use of ultralow-sulfur diesel (ULSD) fuels containing less than about 15 ppm sulfur, as required by regulations in the United States, Europe, and elsewhere, has led to the failure of diesel engine parts such as fuel injectors and pumps because they are lubricated by the fuel itself (Knothe, G., and K. R. Steidley, Energy & Fuels, 19: 1192-1200 (2005); Lacey, P. I., and S. R. Westbrook, Lubricity Requirement of Low Sulfur Diesel Fuels, SAE Tech. Pap. Ser., 950248 (1995); Wei, D., and H. A. Spikes, Wear, 111: 217-235 (1986); Lacey, P. I., and S. J. Lestz, Effect of Low-Lubricity Fuels on Diesel Injection Pumps—Part I: Field Performance, SAE Tech. Pap. Ser., 920823 (1992); Lacey, P. I., and S. J. Lestz, Effect of Low-Lubricity Fuels on Diesel Injection Pumps—Part II: Laboratory Evaluation, SAE Tech. Pap. Ser., 920824 (1992); Nikanjam, M., and P. T. Henderson, Lubricity of Low Sulfur Diesel Fuels, SAE Tech. Pap. Ser., 932740 (1993); Wang, J. C., and D. J. Reynolds, The Lubricity Requirement of Low Sulfur Diesel Fuels, SAE Tech. Pap. Ser., 942015 (1994); Tucker, R. F., et al., The Lubricity of Deeply Hydrogenated Diesel Fuels—The Swedish Experience, SAE Tech. Pap. Ser., 942016 (1994); Wall, S. W., et al., Pet. Coal, 41: 38-42 (1999); Dimitrakis, W. J., Hydrocarbon Eng., 8: 37-39 (2003)). The poor lubricity of ULSD requires additives or blending with another fuel of sufficient lubricity to regain lubricity (Knothe and Steidley, 2005; Lacey and Westbrook, 1995; Wei and Spikes, 1986; Lacey and Lestz, 1992; Lacey and Lestz, 1992; Nikanjam and Henderson, 1993; Wang and Reynolds, 1994; Tucker et al., 1994; Wall et al., 1999; Dimitrakis, 2003). Blending with another fuel necessitates a higher percentage of another fuel of sufficient lubricity to regain lubricity and increases the cost with higher concentration up to about 10-20% (Lacey, P. I., et al., Effects of High Temperature and Pressure on Fuel Lubricated Wear, SAE Tech. Pap. Ser. 2001, 2001-01-3523; Hughes, J. M., et al., Ind. Eng. Chem., 41: 1386-1388 (2002)). For example, improvement of lubricity by blending with biodiesel typically requires at least 1% (10,000 ppm), even better 2% (20,000 ppm), of such fuel (Knothe and Steidley, 2005). Therefore, economically it is better to enhance the lubricity of ULSD by adding additives at additive levels (e.g., <1% instead of ≥1% blend). There is currently a need for better additives for ULSD fuels.

Herein we describe the synthesis of tung oil based fatty acid methyl ester (FAME) which we call EAME. EAME (or other FAME) can be reacted with maleic anhydride through Diels-Alder reaction to form maleation products, named EAME/MA (or other FAME/MA. The EAME/MA (or other FAME/MA) can then be esterified with short chain alcohols to produce a product which can be used, for example, as a diesel additive. Also described are the lubricity data for neat petrodiesel and petrodiesel that contains the esterification products of EAME/MA as additives were evaluated by using the high-frequency reciprocating rig (HFRR) (ASTM D-6079, ISO 12156) lubricity tester.

SUMMARY OF THE INVENTION

Disclosed herein are compositions containing diesel (e.g., containing less than about 15 ppm sulfur) and fatty acid methyl ester/maleic anhydride/esters (FAME/MA/esters), wherein the FAME/MA/esters are prepared by a method involving reacting FAME with MA to form FAME/MA and reacting FAME/MA with alkyl alcohol to form FAME/MA/esters; wherein the FAME is conjugated. The FAME/MA/esters are produced from tung oil or from plant oils in which the unsaturated fatty acids have been converted to conjugated fatty acids. Also disclosed are methods of improving the lubricity of diesel, involving combining diesel and FAME/MA/esters, wherein the FAME/MA/esters are prepared by a method involving reacting FAME with MA to form FAME/MA and reacting FAME/MA with alkyl alcohol to form FAME/MA/esters; wherein the FAME is conjugated.

This summary is provided to introduce a selection of concepts in a simplified form that are further described below in the detailed description. This summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended as an aid in determining the scope of the claimed subject matter.

BRIEF DESCRIPTION OF THE DRAWINGS

The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.

Exemplary FIG. 1 shows the FT-IR spectra of tung oil raw material and chemically modified compounds as described below.

Exemplary FIG. 2 shows the ¹H-NMR of chemically modified compounds as described below.

Exemplary FIG. 3 shows the ¹³C-NMR of chemically modified compounds as described below.

DETAILED DESCRIPTION OF THE INVENTION

Disclosed herein are compositions containing diesel (e.g., containing less than about 15 ppm sulfur) and fatty acid methyl ester/maleic anhydride/esters (FAME/MA/esters), wherein the FAME/MA/esters are prepared by a method involving reacting FAME with MA to form FAME/MA and reacting FAME/MA with alkyl alcohol to form FAME/MA/esters; wherein the FAME is conjugated. The FAME/MA/esters are produced from tung oil or from plant oils in which the unsaturated fatty acids have been converted to conjugated fatty acids. Also disclosed are methods of improving the lubricity of diesel, involving combining diesel and FAME/MA/esters, wherein the FAME/MA/esters are prepared by a method involving reacting FAME with MA to form FAME/MA and reacting FAME/MA with alkyl alcohol to form FAME/MA/esters; wherein the FAME is conjugated.

We have produced tung oil-based fatty acid methyl ester (FAME) which we call EAME because of its high content (e.g., greater than 80%) of eleostearic acid in the tung oil. EAME can be reacted with maleic anhydride through Diels-Alder reaction to form maleation products, named EAME/MA. The EAME/MA can then be esterified with short chain alcohols (e.g., C1-4 alcohols such as methanol, ethanol, butanol, etc.) to produce a diesel additive. An example of the maleation of FAME (e.g., EAME) and esterification of FAME (e.g., EAME) maleation compound is shown in the Scheme below:

The FAME must have conjugated double bonds (i.e., at least two C═C and one single bond between the C═C; —C═C—C═C—) and tung oil is naturally conjugated. Other conjugated FAMEs can be prepared according to methods reported by Larock et al. (Larock, R. C. et al., J. Am. Oil Chem. Soc., 2001, 78: 447-453 (2001)); such conjugated FAMEs include, for example, conjugated vegetable oils, conjugated linoleic acid, and conjugated ethyl linoleate.

These esterified compounds were added into ULSD with concentrations ranging from 100 ppm and 500 ppm and 1000 ppm. Their lubricity was tested by using a high-frequency reciprocating rig (HFRR) lubricity tester (ASTM D-6079, ISO 12156). Lubricity determined per the HFRR test can be evaluated using the lubricity specification for petrodiesel fuel in the petrodiesel standards EN 590 and ASTM D975. The maximum wear scars called for in these petrodiesel standards are 460 μm and 520 μm, respectively. The results show that wear scar diameters of ULSD fuel additized with, for example, EAME/MA esters are reduced by 7%, 40% and 48% with EAME/MA ester concentrations from 100 ppm to 1000 ppm, and frictions are reduced by 6%, 30% and 47%, respectively, compared to the neat ULSD.

Other compounds (e.g., known ULSD additives (e.g., oxidants) known in the art) may be added to the composition provided they do not substantially interfere with the intended activity and efficacy of the composition; whether or not a compound interferes with activity and/or efficacy can be determined, for example, by the procedures utilized below. For example, the phrase “optionally comprising a known ULSD additive” means that the composition may or may not contain a known ULSD additives and that this description includes compositions that contain and do not contain a known ULSD additive. Also, by example, the phrase “optionally adding a known ULSD additive” means that the method may or may not involve adding a known ULSD additive and that this description includes methods that involve and do not involve adding a ULSD additive.

“Optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances in which said event or circumstance occurs and instances where it does not. For example, the phrase “optionally comprising a defoaming agent” means that the composition may or may not contain a defoaming agent and that this description includes compositions that contain and do not contain a defoaming agent. Also, by example, the phrase “optionally adding a defoaming agent” means that the method may or may not involve adding a defoaming agent and that this description includes methods that involve and do not involve adding a defoaming agent.

By the term “effective amount” of a compound or property as provided herein is meant such amount as is capable of performing the function of the compound or property for which an effective amount is expressed. As will be pointed out below, the exact amount required will vary from process to process, depending on recognized variables such as the compounds employed and the processing conditions observed. Thus, it is not possible to specify an exact “effective amount.” However, an appropriate effective amount may be determined by one of ordinary skill in the art using only routine experimentation.

While this invention may be embodied in many different forms, there are described in detail herein specific preferred embodiments of the invention. The present disclosure is an exemplification of the principles of the invention and is not intended to limit the invention to the particular embodiments illustrated. All patents, patent applications, scientific papers, and any other referenced materials mentioned herein are incorporated by reference in their entirety. Furthermore, the invention encompasses any possible combination of some or all of the various embodiments and characteristics described herein and/or incorporated herein. In addition the invention encompasses any possible combination that also specifically excludes any one or some of the various embodiments and characteristics described herein and/or incorporated herein.

The amounts, percentages and ranges disclosed herein are not meant to be limiting, and increments between the recited amounts, percentages and ranges are specifically envisioned as part of the invention. All ranges and parameters disclosed herein are understood to encompass any and all subranges subsumed therein, and every number between the endpoints. For example, a stated range of “1 to 10” should be considered to include any and all subranges between (and inclusive of) the minimum value of 1 and the maximum value of 10 including all integer values and decimal values; that is, all subranges beginning with a minimum value of 1 or more, (e.g., 1 to 6.1), and ending with a maximum value of 10 or less, (e.g. 2.3 to 9.4, 3 to 8, 4 to 7), and finally to each number 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10 contained within the range.

Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions (e.g., reaction time, temperature), percentages and so forth as used in the specification and claims are to be understood as being modified in all instances by the term “about.” Accordingly, unless otherwise indicated, the numerical properties set forth in the following specification and claims are approximations that may vary depending on the desired properties sought to be obtained in embodiments of the present invention. As used herein, the term “about” refers to a quantity, level, value, or amount that varies by as much as 10% to a reference quantity, level, value, or amount.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the preferred methods and materials are now described.

The following examples are intended only to further illustrate the invention and are not intended to limit the scope of the invention as defined by the claims.

Examples

Materials: Tung oil was purchased from Alnor Oil Company, Inc. (Valley Stream, N.Y.). It had a yellow color and a specific gravity of 0.935-0.940 at 25° C. Maleic anhydride (MA) and p-toluenesulfonic acid (PTS) were obtained from Sigma-Aldrich (St. Louis, Mo.). Tung oil fatty acid esters (EAME) were prepared using a transesterification process reported to convert a vegetable oil into biodiesel (Knothe, G., and R. O. Dunn, Biofuels Derived from Vegetable Oils and Fats, IN Oleochemical Manufacture and Applications; Gunstone, F. D., and R. J. Hamilton, Eds; Sheffield Academic Press: Sheffield, U. K., 2001, pp 106-163.)

Preparation of FAME from Tung oil: In a 3 neck round bottom flask fitted with reflux condenser, thermometer and addition port, 50 g of tung oil and 12 ml methanol were added and stirred at 60° C. and 2.78 ml sodium methoxide (25 weight % in methanol) was added and allowed to react for 1 hour. Then the temperature was allowed to fall to room temperature and 50 ml hexane was added. In a separatory funnel the reaction mixture was allowed to separate with the upper layer containing the methyl esters and the lower glycerol layer was removed. The methyl esters were washed with DI water three times until pH neutral, dried over magnesium sulfate, and then filtered. A rotary evaporator was used to remove the hexane and any remaining methanol. The product was named as EAME. Alternatively, C2-C4 alcohols can be used instead of methanol.

Preparation of EAME/MA and Esterification with Methanol and Butanol: First, EAME (9.0 g, 30.8 mmol) and MA (3.17 g, 32.4 mmol) were placed in a 250 mL round-bottom flask equipped with a silicone oil bath and a magnetic stirrer. Nitrogen was bubbled through the mixture for 5 min at room temperature, followed by stirring at 150° C. for 2 h in N₂ atmosphere to give a clear, dark yellow and viscous liquid, termed EAME/MA. In the second step, PTS (180 mg, 2 wt % to EAME/MA) and methanol (10.0 mL, 247.4 mmol, i.e., molar ratio methanol to EAME/MA 8:1) were inserted into the reactor. The reaction mixture was stirred and heated at 65° C. to reflux for 3 h. Then, excess methanol and by-produced water were removed by vacuum-rotary evaporation. 10.0 mL of fresh methanol was added and the same operation repeated twice. Eventually the final product methylated EAME/MA (EAME/MA ester) was obtained through subsequent neutralization, water wash, separations, and vacuum drying. The products were named as EAME/MA/ME. Alternatively, C2-C4 alcohols can be used instead of methanol. In addition, other conjugated FAMEs can be used instead of EAME.

The high-frequency reciprocating rig (HFRR) (ASTM D-6079, ISO 12156) lubricity tester has been used for lubricity tests because the HFRR method is more user-friendly and is also suitable for pressurization to study the lubricity of fuels (Lacey, P. I., et al., Lubricity of Volatile Fuels for Compression Ignition Engines, SAE Tech. Pap. Ser., 2000-01-1804 (2000)). The HFRR method has also been described as being more severe than pump tests (Crockett, R. M., et al., Tribol. Lett., 16: 187-194 (2004)). The prescribed maximum wear scars are 460 μm (60° C.) in the European petrodiesel standard EN 590, and 520 μm (60° C.) in the American petrodiesel standard, ASTM D-975. These standards are used to indicate fuels with sufficient lubricity for practical use in a diesel engine, whereas fuels generating wear scars above those limits may or may not be acceptable.

Lubricity Determination: Lubricity determinations were performed at 60° C. (controlled to less than 1° C.) according to the standard method ASTM D-6079 with an HFRR lubricity tester obtained from PCS Instruments (London, England) via Lazar Scientific (Granger, Ind.). Controlling the humidity to 30%-50% was necessary for the HFRR test to give reproducible results, which was accomplished according to the standard with a potassium carbonate bath (50% humidity). In addition to the usual wear scar data of the HFRR ball, we determined the friction data (coefficient of friction) and film data (electrical resistance) recorded by the software during the experiments.

Characterization: Chemically modified tung oil fatty acid methyl ester (EAME), maleation product (EAMA/MA) and esterification products (EAME/MAME and EAMA/MA/BU) were characterized by FT-IR, ¹H-NMR, and ¹³C-NMR; spectra are shown in FIG. 1, FIG. 2, and FIG. 3, respectively.

In the FTIR spectrum of EAME/MA, the strong peak observed at 1055 cm−1 in FIG. 1 was assigned to the double bond C—H bending of MA. The strong band at 993 cm−1 was attributed to the conjugated double bonds of tung oil and EAME, but this band became a weak absorption peak at EAME/MA and EAME/MA/esters due to the maleation reaction (Liu, C. G., et al., Industrial Crops and Products, 71: 185-196 (2015)). The typical anhydride C═O stretching of MA were found at 1849 and 1776 cm−1 for EAME/MA, but these two peaks almost disappeared after esterification, the ester C═O stretching peak at 1720 cm−1 became strong as seen in the bio-lubricant spectra.

All starting materials and final products were also examined by ¹H NMR and ¹³C NMR (see FIG. 2 and FIG. 3). It was noted that no peak existed at 7.1 ppm in the ¹H NMR spectrum of the EAMA/MA in FIG. 2, which indicated no unreacted MA was left after purification. New bands appeared around 3.5 ppm which represented the protons at the structures where MA attached onto EAMA. The bands at 5.3-6.4 ppm, which corresponded to the protons on the conjugated triene structures of EAME, decreased significantly due to the maleation reaction between MA and the C═C bonds on the EAME chain. In the ¹³C NMR spectrum (FIG. 3), new bands signals appeared at 44-48 ppm, which represented the connecting structure between MA and the EAME chain. The peaks at 126-136 ppm denoting the C═C bonds on EAME chains also decreased significantly. Finally, two peaks at around 172-174 ppm, which denoted the carbonyl carbons on the attached anhydride groups, appeared at EAME/MA and disappeared at EAMA/MA esters because of esterification. Surprisingly, all these results indicated that MA grafted onto EAME effectively and esterification products were confirmed.

Lubricity: Lubricity was assessed using the ASTM D-6079 (HFRR) method at 60° C. Table 1 gives the wear scar values of ULSD and ULSD with additives. Lubricity as determined per the HFRR test can be evaluated using the lubricity specification in the petrodiesel standard ASTM D975. The low-lubricity ULSD exhibited very poor lubricity in the neat form (Table 1) with a wear scar value of 550 μm. The neat samples of EAME-MA-ME or EAME-MA-BU in Table 1 surprisingly showed excellent lubricity, as demonstrated by the low wear scar values, about 100 μm and 200 μm, respectively. These results prompted us to prepare samples in which, initially, 100 ppm, 500 ppm and 1000 ppm of EAME-MA-ME or EAME-MA-BU were added to the low-lubricity petrodiesel fuels (ULSD). The effect of the lubricity additive in ULSD was clearly visible. It can be seen that both samples surprisingly performed excellently. Adding the samples at 500 ppm appeared to induce sufficient lubricity to low-lubricity ULSD fuel. The additives reduced the wear scar of ULSD by 40%. There appeared to be little to no advantage applying a 1000 ppm level. On the other hand, for friction data, the 1000 ppm level performed a little better than the 500 ppm level, as it was reduced by 46% and 47%, respectively.

Lubricity of two additives, polyalphaolefin PAO-6[cSt] and Kendex® 0150H, have been tested with high-frequency reciprocating rig (HFRR) with EAME compounds. Polyalphaolefin PAO-6 (Durasyn 166) was received from Ineos Oligomers (League City, Tex.) with specifications: specific gravity, 0.828 g/mL (ASTM D 4052); kinematic viscosity at 40 and 100° C., 31.13 and 5.91 cSt, respectively (ASTM D 445); pour point, −66° C. (ASTM D 97). Hydrotreated heavy paraffinic mineral oil (Kendex® 0150H), a Group I base oil, was obtained from American Refining Group (Bradford, Pa.) and had the specifications: specific gravity, 0.864 g/mL (ASTM D 4052); kinematic viscosity at 40 and 100° C., 27 and 5.2 cSt, respectively (ASTM D 445); pour point, <−9° C. (ASTM D 97); sulfur content, <300 ppm (ASTM D 5183, four ball test).

HFRR results are shown in Table 2. It was noticed that with 1000 ppm of EAME-MA-BU, the wear scars surprisingly were reduced 24.5% and 25.6% for 150H GP1 Base Oil and 166 POA, respectively. However, the EAME-MA-ME surprisingly reduced 11.0% and 29.0% for 150H GP1 Base Oil and 166 POA, respectively. The EAME-MA-ME responded better for 166 POA than for 150H GP1 Base Oil.

FAMEs prepared from Linseed oil and Black Currant reacted with maleic acid by ene-reaction, and then carried out ring opening by methanol and butanol. The formed compounds were tested with high-frequency reciprocating rig (HFRR) for ultralow-sulfur diesel (ULSD) fuels. The results showed that lubricity of ULSD with 500 ppm and 1000 ppm concentrations of the formed compounds through ene-reaction surprisingly was not improved. The reason was that fatty acids from Linseed oil and Black Currant are not conjugated fatty acids; thus they reacted with maleic anhydride through ene-reaction, not through Diels-Alder addition. That is why concentration of modified vegetable oils in patent EP 1 093 509 B1 showed that it needs more than 1%, or 2% (10,000 ppm and 20,000 ppm) to blend with biodiesels to improve their lubricity.

Conclusions: Surprisingly, the present results obtained with the high-frequency reciprocating rig (HFRR) lubricity tester gave clear data that short chain esters of EAME-MA compound effectively enhanced the lubricity of ULSD. The lubricity of ULSD at low additive levels (about 500 ppm to about 1000 ppm) surprisingly was greatly improved. The additive concentrations were 200 and 400 times lower than blending biodiesel at 1%-2%.

All of the references cited herein, including U.S. Patents and U.S. Patent Application Publications, are incorporated by reference in their entirety.

Thus, in view of the above, there is described (in part) the following:

A composition comprising (or consisting essentially of or consisting of) diesel and FAME/MA/esters, wherein said FAME/MA/esters are prepared by a method comprising (or consisting essentially of or consisting of) reacting FAME with MA to form FAME/MA and reacting FAME/MA with alkyl alcohol to form FAME/MA/esters; wherein said FAME is conjugated. The above composition, wherein said diesel contains less than about 15 ppm sulfur. The above composition, wherein said FAME/MA/esters are produced from tung oil. The above composition, wherein said FAME/MA/esters are produced from plant oils in which the unsaturated fatty acids have been converted to conjugated fatty acids.

A method of improving the lubricity of diesel, said method comprising (or consisting essentially of or consisting of) combining diesel and FAME/MA/esters, wherein said FAME/MA/esters are prepared by a method comprising (or consisting essentially of or consisting of) reacting FAME with MA to form FAME/MA and reacting FAME/MA with alkyl alcohol to form FAME/MA/esters; wherein said FAME is conjugated. The above method, wherein said diesel contains less than about 15 ppm sulfur.

The term “consisting essentially of” excludes additional method (or process) steps or composition components that substantially interfere with the intended activity of the method (or process) or composition, and can be readily determined by those skilled in the art (for example, from a consideration of this specification or practice of the invention disclosed herein).

The invention illustratively disclosed herein suitably may be practiced in the absence of any element (e.g., method (or process) steps or composition components) which is not specifically disclosed herein. Thus the specification includes disclosure by silence (“Negative Limitations In Patent Claims,” AIPLA Quarterly Journal, Tom Brody, 41(1): 46-47 (2013): “ . . . Written support for a negative limitation may also be argued through the absence of the excluded element in the specification, known as disclosure by silence . . . . Silence in the specification may be used to establish written description support for a negative limitation. As an example, in Ex parte Lin [No. 2009-0486, at 2, 6 (B.P.A.I. May 7, 2009)] the negative limitation was added by amendment . . . . In other words, the inventor argued an example that passively complied with the requirements of the negative limitation . . . was sufficient to provide support . . . . This case shows that written description support for a negative limitation can be found by one or more disclosures of an embodiment that obeys what is required by the negative limitation . . . .”

Other embodiments of the invention will be apparent to those skilled in the art from a consideration of this specification or practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with the true scope and spirit of the invention being indicated by the following claims.

TABLE 1 High-Frequency Reciprocating Rig (HFRR) Data of Petrodiesel and with Additives Wear Scars (μm) Results HFRR (60° C.) Ball Ball Red. Disc Disc Film Red. Sample ID X Y Avg. % X Y % Friction % ULSD neat 557 542 550 540 1318 9 0.448 559 500 530 585 1272 10 0.408 EAME-MA-ME 100 ppm 515 458 487 535 1264 14 0.373 555 485 520 6.9 564 1295 16 0.353 6.4 EAME-MA-ME 500 ppm 279 277 278 321 1117 83 0.343 390 330 360 40.0 407 1167 68 0.255 30.0 EAME-MA-ME 1000 ppm 371 278 325 400 1110 74 0.233 377 281 329 40.0 389 1125 77 0.232 46.0 EAME-MA-BU 100 ppm 513 451 482 514 1231 12 0.382 559 484 522 7.0 546 1255 12 0.405 8.1 EAME-MA-BU 500 ppm 348 283 316 372 1130 71 0.242 321 257 289 40.0 318 1112 87 0.219 46.0 EAME-MA-BU 1000 ppm 304 227 266 312 1053 89 0.231 337 242 290 48.0 372 1081 86 0.220 47.0 EAME-MA-ME Neat 98 83 91 80 1082 97 0.065 116 99 108 85 968 93 0.066 EAME-MA-BU Neat 252 157 205 296 1022 79 0.135 243 142 193 270 1010 87 0.125

TABLE 2 Wear Scars (μm) Results HFRR (60° C.) Ball Ball Red. Disc Disc Film Red. Sample ID X Y Avg. % X Y % Friction % 150H GP1 Base Oil-neat 304 293 299 275 103 64 0.215 301 284 293 288 1108 63 0.213 150H GP1 Base Oil 313 269 291 296 1096 72 0.211 +100 ppm EAME-MA- 309 272 291 1.7 302 1089 77 0.203 3.3 ME 150H GP1 Base Oil 308 259 284 331 1099 75 0.205 +100 ppm EAME-MA- 298 217 258 8.4 321 1053 82 0.197 6.1 ME 150H GP1 Base Oil 304 255 280 284 1089 81 0.204 +100 ppm EAME-MA- 264 230 247 11.0 266 1095 89 0.194 7.0 ME 150H GP1 Base Oil 301 253 277 276 1094 72 0.212 +100 ppm EAME-MA- 330 286 308 1.2 303 1124 61 0.221 0 BU 150H GP1 Base Oil 316 259 288 319 1135 76 0.205 +500 ppm EAME-MA- 274 256 265 6.6 270 1073 80 0.211 2.8 BU 150H GP1 Base Oil 267 125 196 299 1025 92 0.195 +1000 ppm EAME-MA- 282 220 251 24.5 301 1044 86 0.196 8.6 BU Durasyn 166 POA-neat 320 290 305 281 1099 42 0.256 312 281 297 294 1092 42 0.261 Durasyn 166 POA 313 280 297 262 1108 64 0.217 +100 ppm EAME-MA- 314 288 301 0.7 295 1110 47 0.246 10.6 ME Durasyn 166 POA 319 277 298 303 1095 59 0.224 +500 ppm EAME-MA- 317 297 307 0 303 1098 58 0.226 13.1 ME Durasyn 166 POA 259 131 195 262 1039 91 0.198 +1000 ppm EAME-MA- 257 206 232 29.0 299 1036 90 0.189 25.3 ME Durasyn 166 POA 305 271 288 269 1093 52 0.231 +100 ppm EAME-MA- 317 263 290 4.0 270 1079 64 0.215 13.9 BU Durasyn 166 POA 339 287 313 328 1130 69 0.216 +500 ppm EAME-MA- 327 263 295 1.0 322 1102 68 0.216 16.6 BU Durasyn 166 POA 261 176 219 254 1025 94 0.193 +1000 ppm EAME-MA- 286 172 229 25.6 285 1027 93 0.194 25.3 BU 

We claim:
 1. A composition comprising diesel and FAME/MA/esters, wherein said FAME/MA/esters are prepared by a method comprising reacting FAME with MA to form FAME/MA and reacting FAME/MA with alkyl alcohol to form FAME/MA/esters; wherein said FAME is conjugated.
 2. The composition according to claim 1, wherein said diesel contains less than about 15 ppm sulfur.
 3. The composition according to claim 1, wherein said FAME/MA/esters are produced from tung oil.
 4. The composition according to claim 1, wherein said FAME/MA/esters are produced from plant oils in which the unsaturated fatty acids have been converted to conjugated fatty acids.
 5. A method of improving the lubricity of diesel, said method comprising combining diesel and FAME/MA/esters, wherein said FAME/MA/esters are prepared by a method comprising reacting FAME with MA to form FAME/MA and reacting FAME/MA with alkyl alcohol to form FAME/MA/esters; wherein said FAME is conjugated.
 6. The method according to claim 5, wherein said diesel contains less than about 15 ppm sulfur. 